CN107366166A - Polyvinyl chloride interior leather for automobiles without genotoxicity and preparation method thereof - Google Patents

Abstract

The invention discloses a kind of polyvinyl chloride interior leather for automobiles of no genotoxicity and preparation method thereof, polyvinyl chloride interior decoration leather without genotoxicity includes polyvinyl chloride epidermis, foam polyvinyl chloride layer and the sealing wax layer coated in polyvinyl chloride epidermis, the sealing wax layer of the present invention is free of N methyl pyrrolidones and N ethyl pyrrolidones, on the premise of environmental requirement and the surface property requirement such as wear-resisting, light shine, heat-resisting, resistant that low VOC and low smell can be met simultaneously, can also not have genotoxicity, avoid to human injury.

Description

Polyvinyl chloride automotive interior leather without reproductive toxicity and preparation method thereof

technical field

The invention relates to the field of leather, in particular to a polyvinyl chloride automotive interior leather without reproductive toxicity and a preparation method thereof.

Background technique

With the continuous development of the automobile industry, people's requirements for automobile environmental protection and safety continue to increase, and the requirements for the smell, VOC, and emission of automobile interior leather are becoming more and more stringent. OEMs have higher and higher environmental protection requirements for automobile interiors. . In automotive interiors, the paint layer on the surface needs to endow the interior leather with special functional requirements and environmental protection requirements: such as excellent wear resistance, scratch resistance, chemical solvent resistance and hand feeling, and low VOC, odor, emission, etc. Both the excellent characteristics of solvent paint and the environmental protection characteristics of water paint are required. The resin and additives of water paint are almost all dispersed in water, prepared into slurry, and then coated. In order to ensure the uniformity and adequacy of mixing, N-ethylpyrrolidone, which is commonly used in this field, is used as an excellent cosolvent in the water. Adding it to the slurry of the water paint layer can increase the solubility on the one hand, and ensure the product stability of the automotive interior leather on the other hand. Reproductive Toxic Substance.

In order to avoid adverse effects of reproductive toxicity, there is an urgent need to develop non-reproductive-toxic automotive interior leather using raw materials that do not contain N-ethylpyrrolidone, so as to meet the requirements of OEMs and final customers on functions, VOC, odor, and environmental protection. etc. requirements.

Contents of the invention

The purpose of the present invention is to overcome the above problems existing in the prior art, and to provide a polyvinyl chloride automotive interior leather without reproductive toxicity, which not only has excellent surface properties, but also has a The product is non-toxic, safer, more stable, less odorous, and more environmentally friendly.

In order to achieve the above-mentioned technical purpose and achieve the above-mentioned technical effect, the present invention is realized through the following technical solutions:

A polyvinyl chloride automotive interior leather without reproductive toxicity is provided, which comprises a polyvinyl chloride cortex, a water paint layer coated on the polyvinyl chloride cortex, and a base cloth attached to the bottom surface of the polyvinyl chloride cortex. The water paint layer is composed of the following components by weight: 20-50 parts of water-based resin, 30-50 parts of water, 5-20 parts of cosolvent, 0.05-1.0 part of amine neutralizer, 0.3-1.0 part of defoamer, 0.5-5 parts of thickener, 0.5-12 parts of hand feeling aid, 4-18 parts of curing agent.

Preferably, the water-based resin is at least one or more of polycarbon-based anionic aliphatic polyurethane, polyester-based aliphatic polyurethane, fatty acid-modified anionic polyurethane, and fluorine-modified acrylic resin. Most water-based resins are water-dispersible (not water-soluble) resins. The selection of such water-based resins is based on the requirements for improving the hydrolysis resistance, yellowing resistance and stain resistance of automotive interior leather.

Preferably, the amine neutralizer is dimethylethanolamine, the purpose of which is to adjust the water paint to be weakly alkaline, so that the weakly acidic thickener can thicken and avoid the growth of microorganisms.

Preferably, the curing agent is at least one or more of hexamethylene diisocyanate-based hydrophilic aliphatic polyisocyanate, cyclohexane-based aliphatic polyisocyanate resin, and polycarbodiimide.

Preferably, the polyvinyl chloride skin layer is composed of the following components by weight: 40-70 parts of PVC powder, 30-60 parts of plasticizer, 5-8 parts of foaming agent, 1-3 parts of stabilizer, 0 parts of pigment ～6 parts, filler 0～3 parts.

Preferably, the foaming agent is composed of the following raw materials in parts by weight: 1-2.5 parts of sodium dodecylsulfonate, 1-2.5 parts of titanate, and 80-100 parts of epoxy resin nanocomposite materials. Titanate is preferably monoalkoxy phosphate titanate coupling agent Tl-411-A, because the compounding between anionic surfactant and amphoteric surfactant can produce significant synergistic effect, the present invention selects ten The composite foaming agent of dialkyl sodium sulfonate and titanate, on the one hand, improves the performance of the surfactant and further enhances the stability of the foam; on the other hand, because the titanate coupling agent Tl-411-A titanium The acid ester itself contains a variety of active groups such as sulfonic acid groups and phosphate groups to endow the foam layer system with a certain degree of cohesiveness.

Preferably, the glue is composed of the following components in parts by weight: 45-60 parts of PVC powder, 40-55 parts of plasticizer, and 1-5 parts of stabilizer.

Compared with the prior art, a kind of polyvinyl chloride automotive interior leather without reproductive toxicity of the present invention has the following advantages:

(1) The water paint layer used in the present invention has no reproductive toxicity, is safer, and is more environmentally friendly. The water paint system does not contain commonly used cosolvents such as N-methylpyrrolidone and N-ethylpyrrolidone strong polar solvents in the industry (both N-methylpyrrolidone and N-ethylpyrrolidone have been listed as reproductively toxic substances by EU regulations), but water is used as a solvent; at the same time, compared with solvent-based paints, it does not contain toxic and harmful solvents (such as Toluene, tetrahydrofuran, etc.), harmless to operators, end users and the environment, while reducing product odor and emissions;

(2) The composition of the water paint layer presents a weak negative charge, while the PVC foam layer presents a variety of groups and charge properties, especially the sulfonic acid groups and phosphate groups contained in the titanate coupling agent. A kind of active group makes the interaction between the two layers and the adhesion is stronger, which meets the quality requirements of the product without pulp loss, no pulp cracking, firm adhesive layer, and wear resistance;

(3) The artificial leather of the present invention can be widely used in automotive interior parts and the like.

Another object of the present invention is to provide a kind of preparation method of polyvinyl chloride automotive upholstery without reproductive toxicity, the method may further comprise the steps:

1) Preparation of PVC slurry: Weigh the raw materials of the PVC cortex according to the formula, mix and stir for 30-60 minutes, and vacuum stir for 5-10 minutes to obtain PVC slurry;

2) Preparation of PVC cortex: apply the PVC slurry prepared in the above step 1) on the release paper, plasticize at 190-210°C for 1-3 minutes; continue to coat a layer of PVC slurry, and plasticize at 190-210°C for 1 minute ~3min; apply glue, and compound a layer of base fabric, then dry at 200~210℃ for 3~5min; tear off the release paper to get the PVC skin layer;

3) printing water paint layer: take the raw material of water paint layer according to formula quantity, mix well, make water paint layer raw material slurry, print water paint layer raw material slurry evenly on PVC cortex, and dry;

4) Embossing: embossing patterns on the paint layer with an embossing roller at a surface temperature of 150-220° C. to obtain the polyvinyl chloride automotive interior leather without reproductive toxicity.

Further, in the step 3), the thickness of the printed water paint layer is 4-20 μm, the drying temperature is 80-120° C., and the printing speed is 15-30 m/min.

Compared with the prior art, the preparation method of a polyvinyl chloride automotive interior leather without reproductive toxicity of the present invention has the following advantages: in the preparation method of the present invention, the adhesion between the water paint layer and the PVC cortex is strong, and the steps are simple. It is suitable for large-scale production and has high production efficiency.

The above description is only an overview of the technical solutions of the present invention. In order to understand the technical means of the present invention more clearly and implement them according to the contents of the description, the specific implementation modes of the present invention are given in detail by the following examples.

detailed description

The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some of the embodiments of the present invention, but not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without creative efforts fall within the protection scope of the present invention.

Example 1:

Weigh the PVC layer components according to the parts by weight of Example 1 in Table 1 below, stir for 30 minutes, vacuumize for 5 minutes, and vacuum stir for 10 minutes to obtain PVC slurry, coat a layer on the release paper, and then heat it under the condition of 190 ° C Plasticize for 2.5 minutes and 200°C for 3 minutes, apply glue and stick it to the base cloth, dry at 200°C for 5 minutes, cool and form, tear off the release paper to obtain the PVC skin.

Weigh the components of the water paint layer according to the parts by weight of Example 1 in Table 2 below, and stir well to form the raw material of the water paint layer, which is evenly printed on the surface of the PVC layer, with a printing speed of 30m/min, a printing thickness of 18μm, and a temperature of 120°C. Dry to cure.

Embossing equipment is used to emboss patterns on PVC with a paint layer, and the embossing temperature is 220 ° C to obtain polyvinyl chloride automotive interior leather without reproductive toxicity.

Example 2:

Weigh the PVC layer components according to the parts by weight of Example 2 in Table 1 below, stir for 60 minutes, vacuumize for 10 minutes, and vacuum stir for 5 minutes to obtain PVC slurry, coat one layer on the release paper, and then heat at 210 ° C Plasticize for 1min, plasticize for 1min at 210°C, apply glue and stick to the base cloth, dry at 200°C for 3min, cool and form, tear off the release paper to obtain the PVC skin.

Weigh the components of the water paint layer according to the weight parts of Example 2 in Table 2 below, and stir well to form a water paint layer raw material, which is evenly printed on the surface of the PVC layer, with a printing speed of 17m/min, a printing thickness of 10μm, and 80°C Dry to cure.

Embossing equipment is used to emboss patterns on PVC with a paint layer, and the embossing temperature is 160°C to obtain polyvinyl chloride automotive interior leather without reproductive toxicity.

Example 3:

Weigh the PVC layer components according to the parts by weight of Example 3 in Table 1 below, stir for 30 minutes, vacuumize for 8 minutes, and vacuum stir for 6 minutes to obtain PVC slurry, coat a layer on the release paper, and then heat at 200 ° C Plasticize for 2.5 minutes, plasticize at 210°C for 3 minutes, apply glue and stick to the base cloth, dry at 210°C for 5 minutes, cool and form, tear off the release paper to obtain the PVC skin.

Weigh the components of the water paint layer according to the parts by weight of Example 3 in Table 2 below, and stir well to form the raw material of the water paint layer, which is evenly printed on the surface of the PVC layer, the printing speed is 20m/min, the printing thickness is 12μm, and 100°C Dry to cure.

Embossing equipment is used to emboss patterns on PVC with a paint layer, and the embossing temperature is 190°C to obtain polyvinyl chloride automotive interior leather without reproductive toxicity.

Comparative example 1

Use the resin containing N-ethylpyrrolidone (using N-ethylpyrrolidone as a cosolvent of the resin) to replace the water-based resin in Example 1, and the others are the same as Example 1.

PVC cortex component content (unit: kg) in each embodiment of table 1

PVC powder plasticizer Foaming agent stabilizer pigment filler Example 1 50 50 5 3 6 1 Example 2 45 55 7 2 4 2 Example 3 60 40 3 1 3 3

Water paint layer component content (unit: kg) in each embodiment of table 2

water-based resin water Amine neutralizer Defoamer thickener Feel Auxiliary Hardener Example 1 50 45 0.8 0.5 1 0 4 Example 2 35 50 0.5 0.5 4 5 5 Example 3 30 30 0.1 0.5 5 12 15

Water paint layer component content (unit: kg) in each embodiment of table 3

Wherein, the blowing agent in the embodiment 1-3 is all made up of the raw material of following weight part: sodium dodecyl sulfonate 2kg, titanate 2kg, epoxy resin nanocomposite material 90kg, all in the embodiment 1-3 The fillers used are all calcium carbonate fillers.

Result verification experiment:

According to the format A of DIN53359/2006-11, test the flex resistance of 200.000 times, test the cleaning resistance according to PV3906, test the scratch resistance according to VDA230-218/2011-01, according to DIN EN ISO 105-B06-3/ Condition 3 of 2004-01 tested light aging, DBL5430/6.3.1/2015-01 tested odor, tested VOC and emission according to DBL 5430/6.2/2015-01, tested friction resistance according to DBL 5306, the above results are shown in Table 3.

Result verification test results Table 3

Obviously, the performance in Examples 1 to 3 is better than Comparative Example 1, although the friction resistance in Example 1 is consistent with the results of Comparative Example, it is obviously better than Comparative Example 1 in terms of odor, VOC and emission, And in embodiment 1, embodiment 2 and embodiment 3 all used water to replace N-ethylpyrrolidone as solvent, and did not use the substance that has reproductive toxicity, guaranteed the environmental protection of product and the advantage of non-reproductive toxicity. Considering that different customers have different requirements for hand feel and frictional resistance, there will still be different formulas to meet the requirements of different customers.

The above description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the present invention will not be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (9)

1. a kind of polyvinyl chloride interior leather for automobiles of no genotoxicity, it includes polyvinyl chloride cortex, coated in the polychlorostyrene second The sealing wax layer of alkene cortex and the base fabric for investing the polyvinyl chloride cortex bottom surface, it is characterised in that：The sealing wax layer is by following The composition composition of parts by weight：20~50 parts of water-base resin, water 30-50 parts, 5~20 parts of cosolvent, amine neutralizer 0.05~1.0 Part, 0.3~1.0 part of defoamer, 0.5~5 part of thickener, 0.5~12 part of feel auxiliary agent, 4~18 parts of curing agent.

2. the polyvinyl chloride interior leather for automobiles of no genotoxicity according to claim 1, it is characterised in that：The water-based tree Fat is the anion aliphatic polyurethane of poly- carbons, the aliphatic polyurethane of polyesters, the poly- ammonia of fatty acid modified anionic At least one of the acrylic resin or a variety of of ester, fluorine richness.

3. the polyvinyl chloride interior leather for automobiles of no genotoxicity according to claim 1, it is characterised in that：The amine neutralizes Agent is dimethylethanolamine.

4. the polyvinyl chloride interior leather for automobiles of no genotoxicity according to claim 1, it is characterised in that：The curing agent For the hydrophilic aliphatic PIC based on hexamethylene diisocyanate, the aliphatic polymeric isocyanate based on hexamethylene At least one of resin, polycarbodiimide are a variety of.

5. the polyvinyl chloride interior leather for automobiles of no genotoxicity according to claim 1, it is characterised in that the polychlorostyrene second Alkene cortex is to be composed of the following components in parts by weight：40~70 parts of PVC powder, 30~60 parts of plasticizer, 5~8 parts of foaming agent, stably 1~3 part of agent, 0~6 part of pigment, 0~3 part of filler.

6. the polyvinyl chloride interior leather for automobiles of no genotoxicity according to claim 5, it is characterised in that：The foaming agent It is made up of the raw material of following parts by weight：1~2.5 part of dodecyl sodium sulfate, 1~2.5 part of titanate esters, epoxide resin nano are compound 80~100 parts of material.

7. a kind of preparation method of the polyvinyl chloride interior leather for automobiles of no genotoxicity, it is characterised in that comprise the following steps：

1) PVC slurries are prepared：The raw material of PVC cortexes is weighed by formula ratio and mixes 30~60min, is stirred under vacuum 5- 10min, obtain PVC slurries；

2) PVC cortexes are prepared：PVC slurries prepared by the step 1) are coated in release liners, 190~210 DEG C of plasticizings 1~ 3min；Continue to apply last layer PVC slurries, 190~210 DEG C of 1~3min of plasticizing；Apply glue, and compound last layer base fabric, then 200~210 DEG C of 3~5min of drying；Tear release liners off, produce PVC cortexes；

3) sealing wax layer is printed：The raw material of sealing wax layer is weighed by formula ratio, is mixed, sealing wax layer raw material slurry is made, on PVC cortexes Sealing wax layer raw material slurry is printed evenly, and is dried；

4) it is embossed：Decorative pattern is suppressed with knurling rolls skin of paint under 150~220 DEG C of surface temperature, produces the no reproduction poison The polyvinyl chloride interior leather for automobiles of property.

8. the preparation method of the polyvinyl chloride interior leather for automobiles of no genotoxicity according to claim 7, it is characterised in that： The thickness of printing sealing wax layer is 4~20 μm in the step 3), drying temperature is 80~120 DEG C, print speed printing speed is 15~30m/ min。

9. the preparation method of the polyvinyl chloride interior leather for automobiles of no genotoxicity according to claim 7, it is characterised in that： The glue is to be composed of the following components in parts by weight：45~60 parts of PVC powder, 40~55 parts of plasticizer, 1~5 part of stabilizer.